Characterization and structures of intermediates in the reactivity of CpWOs3(CO)113-CTol) towards dihydrogen and water

Joon T. Park, Jeong Hee Chung, Hyunjoon Song, Kwangyeol Lee, Jin Ho Lee, Jeong Ran Park, Il Hwan Suh

Research output: Contribution to journalArticle

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Abstract

Initial decarbonylation of CpWOs3(CO) 113-CTol) (1; Cp = η5-C5H5, Tol = p-C6H4Me) with Me3NO/MeCN followed by reaction with dihydrogen and water produces a dihydrido complex CpWOs3(CO)103-CTol)(μ-H)2 (2), a 'butterfly' cluster with a 60 valence electron (VE), and an oxo complex CpWOs3(CO) 10(μ-O)(μ3-CTol) (4) respectively. Complex 2 reacts either with carbon monoxide to produce the starting alkylidyne complex 1 by reductive elimination of dihydrogen or with PPh3 to afford a 62 VE 'butterfly' complex CpWOs3(CO) 10(PPh3)(μ3-CTol)(μ-H)2 (6). Thermolysis of 2 in the presence of water gives a hydrido oxo alkylidene complex, syn-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ,-H) (3a), in which the tolyl substituent on the alkylidene carbon is oriented syn to the μ-oxo ligand. Thermolysis of 4 at 110°C induces decarbonylation to give a tetrahedral alkylidyne complex CpWOs3(CO)9(μ-O)(μ3-CTol) (5), which is reversibly converted back to 4 upon exposure to carbon monoxide. Complex 5 reacts with dihydrogen to afford a mixture of two isomeric hydrido oxo alkylidene complexes, anti-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ-H) (3b,c). The syn-isomer 3a is also produced from a mixture of 3b and 3c by thermolysis in boiling toluene. Compounds 2, 3a,b,c, 4, 5 and 6 have been isolated as crystalline solids and characterized by spectroscopic (IR, MS, 1H and 13C NMR) and analytical data. The structures of 2 and 6 have been determined by single crystal X-ray diffraction studies. Compound 2 crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 14.18(1), b = 28.46(1), c = 13.59(3) Å, V = 5484(13) Å3 and Z = 8. Compound 6 crystallizes in the monoclinic space group P21/n with unit cell parameters a = 19.298(2), b = 22.406(4), c = 9.364(1) Å, β = 92.83(9)°, V = 4044.0(9) Å3 and Z = 4. Diffraction data were collected on a CAD4 diffractometer, and structures were refined to R = 0.0957 and 0.0510 for 2 and 6 respectively. Both 2 and 6 are based upon a 'butterfly' WOs3 metal core with a respective dihedral angle of 114.3(2)° and 113.6(4)° between the W-Os(2)-Os(1) and W-Os(2)-Os(3) planes. Each molecule consists of three Os(CO)3 units and a CpW(CO) fragment, except that the Os(1) center in 6 is additionally coordinated with PPh3. The μ3-alkylidyne caps unsymmetrically the respective W-Os(2)-Os(3) face of both complexes.

Original languageEnglish
Pages (from-to)215-225
Number of pages11
JournalJournal of Organometallic Chemistry
Volume526
Issue number2
DOIs
Publication statusPublished - 1996 Dec 27
Externally publishedYes

Fingerprint

alkylidene
Butterflies
Thermolysis
reactivity
Carbon Monoxide
Carbon monoxide
carbon monoxide
Water
Electrons
water
valence
Diffractometers
Toluene
Dihedral angle
cells
diffractometers
diffraction
caps
X-Ray Diffraction
Isomers

Keywords

  • μ-Oxo complexes
  • Carbonyl
  • Metal clusters
  • Tungsten-triosmium
  • X-ray structure

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Characterization and structures of intermediates in the reactivity of CpWOs3(CO)113-CTol) towards dihydrogen and water. / Park, Joon T.; Chung, Jeong Hee; Song, Hyunjoon; Lee, Kwangyeol; Lee, Jin Ho; Park, Jeong Ran; Suh, Il Hwan.

In: Journal of Organometallic Chemistry, Vol. 526, No. 2, 27.12.1996, p. 215-225.

Research output: Contribution to journalArticle

Park, Joon T. ; Chung, Jeong Hee ; Song, Hyunjoon ; Lee, Kwangyeol ; Lee, Jin Ho ; Park, Jeong Ran ; Suh, Il Hwan. / Characterization and structures of intermediates in the reactivity of CpWOs3(CO)113-CTol) towards dihydrogen and water. In: Journal of Organometallic Chemistry. 1996 ; Vol. 526, No. 2. pp. 215-225.
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title = "Characterization and structures of intermediates in the reactivity of CpWOs3(CO)11(μ3-CTol) towards dihydrogen and water",
abstract = "Initial decarbonylation of CpWOs3(CO) 11(μ3-CTol) (1; Cp = η5-C5H5, Tol = p-C6H4Me) with Me3NO/MeCN followed by reaction with dihydrogen and water produces a dihydrido complex CpWOs3(CO)10(μ3-CTol)(μ-H)2 (2), a 'butterfly' cluster with a 60 valence electron (VE), and an oxo complex CpWOs3(CO) 10(μ-O)(μ3-CTol) (4) respectively. Complex 2 reacts either with carbon monoxide to produce the starting alkylidyne complex 1 by reductive elimination of dihydrogen or with PPh3 to afford a 62 VE 'butterfly' complex CpWOs3(CO) 10(PPh3)(μ3-CTol)(μ-H)2 (6). Thermolysis of 2 in the presence of water gives a hydrido oxo alkylidene complex, syn-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ,-H) (3a), in which the tolyl substituent on the alkylidene carbon is oriented syn to the μ-oxo ligand. Thermolysis of 4 at 110°C induces decarbonylation to give a tetrahedral alkylidyne complex CpWOs3(CO)9(μ-O)(μ3-CTol) (5), which is reversibly converted back to 4 upon exposure to carbon monoxide. Complex 5 reacts with dihydrogen to afford a mixture of two isomeric hydrido oxo alkylidene complexes, anti-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ-H) (3b,c). The syn-isomer 3a is also produced from a mixture of 3b and 3c by thermolysis in boiling toluene. Compounds 2, 3a,b,c, 4, 5 and 6 have been isolated as crystalline solids and characterized by spectroscopic (IR, MS, 1H and 13C NMR) and analytical data. The structures of 2 and 6 have been determined by single crystal X-ray diffraction studies. Compound 2 crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 14.18(1), b = 28.46(1), c = 13.59(3) {\AA}, V = 5484(13) {\AA}3 and Z = 8. Compound 6 crystallizes in the monoclinic space group P21/n with unit cell parameters a = 19.298(2), b = 22.406(4), c = 9.364(1) {\AA}, β = 92.83(9)°, V = 4044.0(9) {\AA}3 and Z = 4. Diffraction data were collected on a CAD4 diffractometer, and structures were refined to R = 0.0957 and 0.0510 for 2 and 6 respectively. Both 2 and 6 are based upon a 'butterfly' WOs3 metal core with a respective dihedral angle of 114.3(2)° and 113.6(4)° between the W-Os(2)-Os(1) and W-Os(2)-Os(3) planes. Each molecule consists of three Os(CO)3 units and a CpW(CO) fragment, except that the Os(1) center in 6 is additionally coordinated with PPh3. The μ3-alkylidyne caps unsymmetrically the respective W-Os(2)-Os(3) face of both complexes.",
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TY - JOUR

T1 - Characterization and structures of intermediates in the reactivity of CpWOs3(CO)11(μ3-CTol) towards dihydrogen and water

AU - Park, Joon T.

AU - Chung, Jeong Hee

AU - Song, Hyunjoon

AU - Lee, Kwangyeol

AU - Lee, Jin Ho

AU - Park, Jeong Ran

AU - Suh, Il Hwan

PY - 1996/12/27

Y1 - 1996/12/27

N2 - Initial decarbonylation of CpWOs3(CO) 11(μ3-CTol) (1; Cp = η5-C5H5, Tol = p-C6H4Me) with Me3NO/MeCN followed by reaction with dihydrogen and water produces a dihydrido complex CpWOs3(CO)10(μ3-CTol)(μ-H)2 (2), a 'butterfly' cluster with a 60 valence electron (VE), and an oxo complex CpWOs3(CO) 10(μ-O)(μ3-CTol) (4) respectively. Complex 2 reacts either with carbon monoxide to produce the starting alkylidyne complex 1 by reductive elimination of dihydrogen or with PPh3 to afford a 62 VE 'butterfly' complex CpWOs3(CO) 10(PPh3)(μ3-CTol)(μ-H)2 (6). Thermolysis of 2 in the presence of water gives a hydrido oxo alkylidene complex, syn-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ,-H) (3a), in which the tolyl substituent on the alkylidene carbon is oriented syn to the μ-oxo ligand. Thermolysis of 4 at 110°C induces decarbonylation to give a tetrahedral alkylidyne complex CpWOs3(CO)9(μ-O)(μ3-CTol) (5), which is reversibly converted back to 4 upon exposure to carbon monoxide. Complex 5 reacts with dihydrogen to afford a mixture of two isomeric hydrido oxo alkylidene complexes, anti-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ-H) (3b,c). The syn-isomer 3a is also produced from a mixture of 3b and 3c by thermolysis in boiling toluene. Compounds 2, 3a,b,c, 4, 5 and 6 have been isolated as crystalline solids and characterized by spectroscopic (IR, MS, 1H and 13C NMR) and analytical data. The structures of 2 and 6 have been determined by single crystal X-ray diffraction studies. Compound 2 crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 14.18(1), b = 28.46(1), c = 13.59(3) Å, V = 5484(13) Å3 and Z = 8. Compound 6 crystallizes in the monoclinic space group P21/n with unit cell parameters a = 19.298(2), b = 22.406(4), c = 9.364(1) Å, β = 92.83(9)°, V = 4044.0(9) Å3 and Z = 4. Diffraction data were collected on a CAD4 diffractometer, and structures were refined to R = 0.0957 and 0.0510 for 2 and 6 respectively. Both 2 and 6 are based upon a 'butterfly' WOs3 metal core with a respective dihedral angle of 114.3(2)° and 113.6(4)° between the W-Os(2)-Os(1) and W-Os(2)-Os(3) planes. Each molecule consists of three Os(CO)3 units and a CpW(CO) fragment, except that the Os(1) center in 6 is additionally coordinated with PPh3. The μ3-alkylidyne caps unsymmetrically the respective W-Os(2)-Os(3) face of both complexes.

AB - Initial decarbonylation of CpWOs3(CO) 11(μ3-CTol) (1; Cp = η5-C5H5, Tol = p-C6H4Me) with Me3NO/MeCN followed by reaction with dihydrogen and water produces a dihydrido complex CpWOs3(CO)10(μ3-CTol)(μ-H)2 (2), a 'butterfly' cluster with a 60 valence electron (VE), and an oxo complex CpWOs3(CO) 10(μ-O)(μ3-CTol) (4) respectively. Complex 2 reacts either with carbon monoxide to produce the starting alkylidyne complex 1 by reductive elimination of dihydrogen or with PPh3 to afford a 62 VE 'butterfly' complex CpWOs3(CO) 10(PPh3)(μ3-CTol)(μ-H)2 (6). Thermolysis of 2 in the presence of water gives a hydrido oxo alkylidene complex, syn-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ,-H) (3a), in which the tolyl substituent on the alkylidene carbon is oriented syn to the μ-oxo ligand. Thermolysis of 4 at 110°C induces decarbonylation to give a tetrahedral alkylidyne complex CpWOs3(CO)9(μ-O)(μ3-CTol) (5), which is reversibly converted back to 4 upon exposure to carbon monoxide. Complex 5 reacts with dihydrogen to afford a mixture of two isomeric hydrido oxo alkylidene complexes, anti-CpWOs3(CO)9(μ-O)(μ-CHTol)(μ-H) (3b,c). The syn-isomer 3a is also produced from a mixture of 3b and 3c by thermolysis in boiling toluene. Compounds 2, 3a,b,c, 4, 5 and 6 have been isolated as crystalline solids and characterized by spectroscopic (IR, MS, 1H and 13C NMR) and analytical data. The structures of 2 and 6 have been determined by single crystal X-ray diffraction studies. Compound 2 crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 14.18(1), b = 28.46(1), c = 13.59(3) Å, V = 5484(13) Å3 and Z = 8. Compound 6 crystallizes in the monoclinic space group P21/n with unit cell parameters a = 19.298(2), b = 22.406(4), c = 9.364(1) Å, β = 92.83(9)°, V = 4044.0(9) Å3 and Z = 4. Diffraction data were collected on a CAD4 diffractometer, and structures were refined to R = 0.0957 and 0.0510 for 2 and 6 respectively. Both 2 and 6 are based upon a 'butterfly' WOs3 metal core with a respective dihedral angle of 114.3(2)° and 113.6(4)° between the W-Os(2)-Os(1) and W-Os(2)-Os(3) planes. Each molecule consists of three Os(CO)3 units and a CpW(CO) fragment, except that the Os(1) center in 6 is additionally coordinated with PPh3. The μ3-alkylidyne caps unsymmetrically the respective W-Os(2)-Os(3) face of both complexes.

KW - μ-Oxo complexes

KW - Carbonyl

KW - Metal clusters

KW - Tungsten-triosmium

KW - X-ray structure

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